WO2010151041A2 - Composition pour un film de revêtement soluble dans l'eau - Google Patents

Composition pour un film de revêtement soluble dans l'eau Download PDF

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Publication number
WO2010151041A2
WO2010151041A2 PCT/KR2010/004069 KR2010004069W WO2010151041A2 WO 2010151041 A2 WO2010151041 A2 WO 2010151041A2 KR 2010004069 W KR2010004069 W KR 2010004069W WO 2010151041 A2 WO2010151041 A2 WO 2010151041A2
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WO
WIPO (PCT)
Prior art keywords
water
coating film
soluble
polymer
composition
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PCT/KR2010/004069
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English (en)
Korean (ko)
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WO2010151041A3 (fr
Inventor
이정열
장유진
이재우
김재현
Original Assignee
주식회사 동진쎄미켐
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Publication of WO2010151041A2 publication Critical patent/WO2010151041A2/fr
Publication of WO2010151041A3 publication Critical patent/WO2010151041A3/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a composition for a water-soluble coating film, and more particularly, to a water-soluble coating film capable of adjusting top-loss of photoresist film and pattern and improving line edge roughness (LER) using the same. It relates to a composition for.
  • a photolithography process capable of forming an ultrafine photoresist pattern having a line width of 80 nm or less is required.
  • a photoresist composition containing a photosensitive polymer and a solvent is coated on a substrate such as a silicon wafer used for fabricating an integrated circuit, and heated to bake the solvent to evaporate the thin film.
  • a photoresist film in the form of a film is formed.
  • the chemical properties of the photosensitive polymer change in the exposed region.
  • the exposed photoresist film is treated with a developer solution to selectively dissolve and remove portions of the exposed or unexposed photoresist film to form a photoresist pattern.
  • a self-aligned double patterning technology forms a second photoresist pattern by forming a boundary layer (CAP) on the first photoresist pattern, a second photoresist film thereon, and then removing the boundary layer, and forming a photoresist. It is to increase the resolution of the pattern.
  • CAP boundary layer
  • TMAH tetramethyl ammonium hydroxide
  • an object of the present invention is a composition for water-soluble coating film which can control the top-loss of the photoresist film and the pattern by using a coating film which can diffuse an acid by a heating process and dissolve in water or a developing solution.
  • Another object of the present invention is to provide a composition for a water-soluble coating film which can improve line edge roughness (LER) of a photoresist pattern.
  • LER line edge roughness
  • the present invention 1 to 30% by weight of a water-soluble polymer; 0.1 to 300 parts by weight of an acid compound selected from the group consisting of organic acids, inorganic acids and mixtures thereof, based on 100 parts by weight of the water-soluble polymer; 0.1 to 50 parts by weight of an organic base, based on 100 parts by weight of the water-soluble polymer; And a remaining solvent, on the photoresist film and the pattern, to form an aqueous coating film that can diffuse an acid by a heating process and be dissolved in water or a developer, thereby reducing the thickness of the photoresist film and the pattern, It provides a composition for a water-soluble coating film.
  • the composition for water-soluble coating film according to the present invention by using a coating film that can diffuse the acid by the heating process, and can be dissolved in water or developer, it is possible to control the top-loss of the photoresist film and pattern, When the water-soluble coating film is formed on the photoresist pattern, the line edge roughness (LER) and the line width roughness (LWR) of the photoresist pattern may be improved by heating.
  • LER line edge roughness
  • LWR line width roughness
  • DPT double patterning technology
  • CAP boundary layer
  • 1 is a graph showing the acid diffusion distance (nm) by the water-soluble coating film according to Examples 2-1 to 2-67.
  • FIG. 2 is a graph showing line edge roughness (LER) reduction amount (nm) of the photoresist pattern according to Examples 3-1 to 3-23 and Comparative Example 2.
  • LER line edge roughness
  • composition for water-soluble coating film according to the present invention on the photoresist film and the pattern, by forming a water-soluble coating film that can disperse the acid by the heating process and soluble in water or developer, reducing the thickness of the photoresist film and pattern (top- It is possible to control loss and improve line edge roughness (LER) using the same, and includes acid compounds, organic bases, and solvents selected from the group consisting of water-soluble polymers, organic acids, inorganic acids, and mixtures thereof.
  • LER line edge roughness
  • the water-soluble polymer used in the present invention can form a coating film, and is a polymer having water solubility, for example, a conventional acrylic polymer, vinyl polymer, cellulose derivative, alkylene polymer, glycol polymer, urea having water solubility.
  • Type polymers, melamine type polymers, epoxy type polymers, mixtures thereof, and the like can be used, and preferably water-soluble acrylic polymers or vinyl polymers can be used.
  • Specific examples of the water-soluble polymer polyacrylic acid (PAA), polyvinyl alcohol (polyvinylalcohol: PVA), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyurethane (PU) ) May be exemplified.
  • the content of the water-soluble polymer in the water-soluble coating film composition is 1 to 30% by weight, preferably 3 to 10% by weight. If the content of the water-soluble polymer is less than 1% by weight, there is a risk that the coating film formation is difficult, if it exceeds 30% by weight, acid diffusion becomes difficult during heating, or when removing the water-soluble coating film, there is a fear that it is difficult to remove.
  • an acid can be diffused from a coating film into a photoresist film, a pattern, and the like during heating, and a common organic acid, an inorganic acid, a mixture thereof, and the like can be used.
  • an organic acid (carboxylic acid, sulfonic acid) represented by General formula (2) can be used.
  • R 1 and R 2 are each independently hydrogen, a substituted or unsubstituted C 1 to 15, preferably a linear or branched alkyl group of 1 to 13, substituted or unsubstituted 4 15 to 15, preferably 5 to 14 cyclic alkyl or aryl groups, for example, hydrogen, methyl, ethyl, propyl, isopropyl, butyl, phenyl, hexyl, cyclohexyl, toluene, benzyl Group, 4-methyl cyclohexyl group, xylene group, naphthalene group, adamantane group, camphor group, methyladamantane group, (1-cyclohethoxy-ethoxy) -benzene group, benzene ester group, trifluoromethyl group, Nonafluoro butyl group etc. can be illustrated.
  • the content of the acid compound is 0.1 to 300 parts by weight, preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, most preferably 10 to 50 parts by weight, based on 100 parts by weight of the water-soluble polymer. to be. If the amount of the acid compound is too small, the acid diffusion into the lower layer (photoresist film / pattern) may not be easy and may not cause a top-loss effect. If the amount is too high, the lower layer may be formed by acid. There is a fear that the shape of the pattern may be deteriorated due to the increase in the acid diffusion length of the and the increase in the amount of top-loss.
  • the organic base used in the present invention is added in order to control acid diffusion by the acid compound, and may be a conventional organic base, and preferably includes nitrogen such as organic amine, and carbon and / or oxygen
  • Organic base consisting of, more preferably, monoethanolamine (monoethanolamine (MEOA), diethanolamine (diethanolamine (DEOA), triethanolamine (TEOA), triethylamine (triethylamine (TEA), triprophylamine : TPA), tripenthylamine (TPeA), di-isoprophyl aniline (DIPAn), compounds thereof and the like can be used.
  • the content of the organic base is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably 1 to 10 parts by weight based on 100 parts by weight of the water-soluble polymer. If the content of the organic base is too high, the acid diffusion length of the lower film quality is increased by the acid, and the shape of the pattern may be poor due to the increase in the amount of top-loss. If the content is too small, the acid to the lower film quality may be reduced. There is a fear that the diffusion is not easy to cause a top-loss effect.
  • solvent used in the present invention those which do not affect the photoresist film and the pattern when coating and forming the coating film may be used.
  • deionized water, lower alcohols having 1 to 10 carbon atoms, and mixtures thereof may be used.
  • the water-soluble coating film composition according to the present invention may further include a conventional surfactant to increase the uniformity of the coating film.
  • the surfactant may be a water-soluble anionic surfactant, cationic surfactant or amphoteric surfactant, for example, alkylbenzene sulfonate-based surfactant, higher amine halide, quaternary ammonium salt-based surfactant, alkylpyridinium salt-based interface
  • An activator, an amino acid type surfactant, sulfonimide type surfactant, etc. can be used.
  • the content of the surfactant is 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the total water-soluble coating film composition. If the content of the surfactant is less than 0.01 parts by weight based on 100 parts by weight of the total water-soluble coating film composition, there is a possibility that the uniformity of the coating film is lowered when forming the coating film, if it exceeds 2 parts by weight, the coating film is removed with water or developer In the process of increasing the loss of the film (coating film) it can not effectively form a coating film in the primary pattern.
  • the water-soluble coating film formed by the composition for water-soluble coating film according to the present invention by controlling the thickness of the coating film and the content of the composition, to control the top-loss of the photoresist film and pattern (line edge roughness using the same) Roughness (LER) can be improved.
  • the water-soluble coating film for example, can be formed on the photoresist film or pattern to reduce the thickness or improve the line edge roughness to a thickness of 0.1 to 30nm in general, such as by coating, spin coating, etc. Soft bake at a temperature of 50 to 150 ° C.
  • TMAH tetramethyl ammonium hydroxide
  • PAA polyacrylic acid
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • TEOA triethanolamine
  • MEOA monoethanolamine
  • TEA triethylamine
  • IPA isopropyl alcohol
  • a photoresist film was formed by coating DHA-3606 (ArF photoresist composition, manufactured by Dongjin Semichem Co., Ltd.) at a thickness of 200 nm on the wafer etching layer. After coating the water-soluble coating film composition prepared in Examples 1-1 to 1-67 on the photoresist film to form a 200nm-thick water-soluble coating film (thin film containing acid), the oven or 110 °C After 90 seconds of soft bake on the hot plate, the heated wafer was immersed in an aqueous 2.38 wt% tetramethyl ammonium hydroxide (TMAH) solution for 60 seconds and developed on the ArF photoresist film. Thickness reduction (top loss) occurred.
  • TMAH tetramethyl ammonium hydroxide
  • Comparative Example 1 a water-soluble coating film was not formed on top of the photoresist film, and developed by immersing in a 2.38 wt% TMAH aqueous solution for 60 seconds.
  • the thickness reduction (top-loss, acid diffusion distance) of the photoresist film was investigated, and the results are shown in Table 2 below.
  • the acid diffusion distance (thickness reduction, top-loss) by each of the water-soluble coating films (Examples 2-1 to 2-67) is shown graphically.
  • a photoresist film was formed by coating DHA-3606 (ArF photoresist, Dongjin Semichem Co., Ltd.) at a thickness of 200 nm on the wafer etching layer. After forming a 70 nm line and space (L / S) line using an exposure machine (ASML 1200, manufacturer: ASML) having a numerical aperture of 0.85 in the photoresist film, Examples 1-1 to 1-23 Spin-coating the water-soluble coating film composition prepared in the above on the wafer on which the photoresist pattern was formed to a thickness of 200 nm to form a water-soluble coating film, followed by soft heat treatment for 90 seconds in an oven or hot plate at 90 ° C.
  • DHA-3606 ArF photoresist, Dongjin Semichem Co., Ltd.
  • the line edge roughness (LER) of the pattern was reduced (improved).
  • Comparative Example 2 without developing a water-soluble coating film on the photoresist pattern, it was developed by immersing in 2.38% by weight aqueous TMAH solution for 60 seconds.
  • the change amount and the decrease of the LER of the line CD (critical dimension, line width) of the photoresist pattern were measured, and the results are shown in Table 3 below.
  • the LER reduction amount (nm) of the photoresist patterns is shown graphically in FIG. 2.
  • the water-soluble coating film composition according to the present invention can be applied to a conventional photoresist film or pattern to form a coating film, by performing soft baking and development, induce top-loss And it can be seen that it is possible to improve the LER using it, it can be seen that through the selection of the acid compound, etc., it is possible to control the amount of reduction of the top-loss and LER.
  • a DPT process such as self-aligned double patterning technology (SADPT) can be effectively performed by a simple method.
  • composition for water-soluble coating film according to the present invention by using a coating film that can diffuse the acid by the heating process, and can be dissolved in water or developer, it is possible to control the top-loss of the photoresist film and pattern, It is useful for double patterning technology (DPT), such as self-aligned double patterning technology (SaDPT).
  • DPT double patterning technology
  • SaDPT self-aligned double patterning technology

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Paints Or Removers (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une composition pour un film de revêtement soluble dans l'eau qui permet d'ajuster l'épaisseur des films et des motifs de photorésine et d'améliorer la rugosité de bord de ligne (LER). La composition pour un film de revêtement soluble dans l'eau comprend : 1 à 30 % en poids d'un polymère soluble dans l'eau; 0,1 à 300 parties en poids d'un composé acide sélectionné dans un groupe comprenant l'acide organique, l'acide inorganique et un mélange de ceux-ci, par rapport à 100 parties en poids du polymère soluble dans l'eau; 0,1 à 50 parties en poids d'une base organique par rapport à 100 parties en poids du polymère soluble dans l'eau, le reste étant un solvant. La présente invention diffuse l'acide par un processus chauffant et forme un film de revêtement soluble dans l'eau qui est soluble dans l'eau ou dans une solution de révélateur pour permettre une réduction d'épaisseur sur des films et des motifs de photorésine.
PCT/KR2010/004069 2009-06-24 2010-06-23 Composition pour un film de revêtement soluble dans l'eau WO2010151041A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2009-0056352 2009-06-24
KR1020090056352A KR20100138020A (ko) 2009-06-24 2009-06-24 수용성 코팅막용 조성물

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WO2010151041A2 true WO2010151041A2 (fr) 2010-12-29
WO2010151041A3 WO2010151041A3 (fr) 2011-04-14

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040053511A1 (en) * 2002-09-16 2004-03-18 Manish Chandhok Line edge roughness reduction
KR20060074585A (ko) * 2004-12-27 2006-07-03 주식회사 하이닉스반도체 감광막 패턴 수축용 조성물
KR20060074746A (ko) * 2004-12-28 2006-07-03 주식회사 하이닉스반도체 감광막 패턴 수축용 조성물
KR100715600B1 (ko) * 2005-12-28 2007-05-10 동부일렉트로닉스 주식회사 반도체소자의 미세패턴 형성방법
KR20070075817A (ko) * 2006-01-16 2007-07-24 주식회사 하이닉스반도체 포토레지스트 패턴 축소용 수용성 중합체, 상기 수용성중합체를 포함하는 포토레지스트 패턴 축소용 조성물 및상기 조성물을 이용한 미세패턴 형성 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040053511A1 (en) * 2002-09-16 2004-03-18 Manish Chandhok Line edge roughness reduction
KR20060074585A (ko) * 2004-12-27 2006-07-03 주식회사 하이닉스반도체 감광막 패턴 수축용 조성물
KR20060074746A (ko) * 2004-12-28 2006-07-03 주식회사 하이닉스반도체 감광막 패턴 수축용 조성물
KR100715600B1 (ko) * 2005-12-28 2007-05-10 동부일렉트로닉스 주식회사 반도체소자의 미세패턴 형성방법
KR20070075817A (ko) * 2006-01-16 2007-07-24 주식회사 하이닉스반도체 포토레지스트 패턴 축소용 수용성 중합체, 상기 수용성중합체를 포함하는 포토레지스트 패턴 축소용 조성물 및상기 조성물을 이용한 미세패턴 형성 방법

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WO2010151041A3 (fr) 2011-04-14
KR20100138020A (ko) 2010-12-31

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